The recently developed generalized Mulliken-Hush approach for the calculation of the electronic coupling matrix element for electron-transfer processes is applied to two rigidly linked donor-bridge-acceptor systems having dimethoxyanthracene as the donor and a dicarbomethoxycyclobutene unit as the acceptor. The dependence of the electronic coupling matrix element as a function of bridge type is examined with and without solvent molecules present. For clamp-shaped bridge structures solvent can have a dramatic effect on the electronic coupling matrix element. The behavior with variation of solvent is in good agreement with that observed experimentally for these systems.
© 1995 American Chemical Society
Cave, R.J.; Newton, M.D.; Kumar, K.; Zimmt, M.B. "Theoretical Study of Solvent Effects on the Electronic Coupling Element in Rigidly Linked Donor-Acceptor Systems,” J. Phys. Chem. 1995, 99, 17501. doi: 10.1021/j100049a006